US4208208A - Nickel alloy base metal plate for directly heated oxide cathodes - Google Patents

Nickel alloy base metal plate for directly heated oxide cathodes Download PDF

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US4208208A
US4208208A US05/961,272 US96127278A US4208208A US 4208208 A US4208208 A US 4208208A US 96127278 A US96127278 A US 96127278A US 4208208 A US4208208 A US 4208208A
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base metal
metal plate
tungsten
weight
rhenium
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US05/961,272
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Akira Misumi
Masaharu Kumada
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Hitachi Ltd
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Hitachi Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/13—Solid thermionic cathodes
    • H01J1/15—Cathodes heated directly by an electric current
    • H01J1/18—Supports; Vibration-damping arrangements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • This invention relates to a base metal plate material for a directly heated oxide cathode.
  • a cathode for a television picture tube there has been mainly used an indirectly heated cathode wherein a time required for the appearance of an image from the beginning of receiving a television signal is shortened by always allowing flow of a preheating electric current through a heater even during a non-operation period and by raising a heater current value to a rating value at the time of receiving the television signal.
  • a quick operating type cathode which requires no preheating but a short time from the beginning of a heater current flow to the appearance of the image has been required.
  • the indirectly heated cathode it generally requires about 20 seconds from the beginning of a heater current flow to the appearance of the image in the case of no flow of a preheating current.
  • the time required for the appearance of the image from the beginning of a heating current flow can be shortened to 1 to 2 seconds if properly designed.
  • Such a cathode is suitable for the quick operating type cathode.
  • numeral 1 denotes a base which is heated by the supply of an electric current
  • numeral 2 denotes terminals for supplying the electric current
  • numeral 3 denotes a so-called oxide.
  • the base 1 a material having high specific electric resistance so as to consume much electric energy in a small part of the electric current path.
  • the base In order to control the temperature of the base made of such a material as mentioned above within a temperature range suitable for an oxide cathode, the base should have a form which has a longer periphery with respect to the cross-sectional area surrounded by the periphery.
  • the base is preferably made, for example, of a thin strip of such a material as mentioned above having a thickness of 100 ⁇ m or less, more preferably 60 ⁇ m or less.
  • the material for the base should have sufficient mechanical strength at high temperatures in order to maintain the form having such a cross-section as mentioned above within the cathode operating temperature range.
  • the base material should have, as one of its important properties, the property of being suitable for causing sufficient electrons for a long period of time to be emitted from one or more so-called oxides such as barium oxide or a mixture of barium oxide and other oxides of alkaline earth metals, e.g. Ca, Sr, etc. coated on the surface of the base.
  • alloys containing nickel as a main component together with either one or both of tungsten and molybdenum which are excellent in heat resistance and trace amounts of one or more reducing agents have been used experimentally and experientially as a base metal for directly heated oxide cathodes (e.g. Japanese Patent Appln. Kokai (Laid-Open) Nos. 57771/77, 39054/78 and 39055/78).
  • a base metal for directly heated oxide cathodes e.g. Japanese Patent Appln. Kokai (Laid-Open) Nos. 57771/77, 39054/78 and 39055/78.
  • problems such as a large amount of a so-called interface layer due to tungsten or molybdenum being produced between the base and the oxide layer during the picture tube production process or the usage of the thus produced picture tube, and more often resulting in peeling of the oxide layer.
  • rhenium which does not form an interface layer by itself between the base and the oxide layer is added to a nickel-tungsten alloy for improving mechanical strength at high temperatures and specific electric resistance.
  • the present invention provides a base metal plate material for a directly heated oxide cathode which comprises nickel as a main component, rhenium and tungsten, and if desired, a small amount of at least one reducing agent.
  • the base metal plate is made of an alloy comprising nickel as a main component, rhenium and tungsten.
  • a preferable amount of rhenium in the alloy is in the range from 4 to 17% by weight. If the amount of rhenium is too low, mechanical strength at high temperatures and specific electric resistance of the base become insufficient, while if the amount of rhenium is too much, rhenium is to be precipitated in the course of repeating temperature rise and cooling.
  • a preferable amount of tungsten in the alloy is in the range from 1 to 6% by weight.
  • the presence of tungsten in such a range as mentioned above does not cause formation of an interface layer due to tungsten and peeling of the oxide layer. Since tungsten functions in such a manner as to maintain an electron emissive ability of the oxide cathode after the exhaustion of the reducing agent if contained or from the beginning if the reducing agent is not contained, the presence of tungsten produces very desirable results. If the amount of tungsten is too low, the effect of tungsten as mentioned above is insufficient, while if the amount of tungsten is too much, an interface layer due to tungsten is to be formed.
  • rhenium and tungsten seem to be dependent on mutual effects of these components.
  • a more preferable range of rhenium is from 4 to 14% by weight
  • a more preferable range of rhenium is from 9 to 17% by weight. Therefore, the amount of rhenium in the range from 9 to 14% by weight is more preferable irrespective of the tungsten content in the range of 1-6% by weight.
  • the amount of nickel in the alloy is the rest of the total of rhenium and tungsten.
  • the base metal alloy may further contain at least one reducing agent such as zirconium, magnesium, silicon, aluminum and the like.
  • zirconium it is preferable to use zirconium in an amount of 5-6% by weight or less based on the weight of the alloy. If the amount is too much, a eutectic having a lower melting point will be produced to lower mechanical strength at high temperatures.
  • an impurity amount of one or more these reducing agents corresponding to an amount contained in a conventional base metal for an oxide cathode as an impurity, can usually be used together with or without zirconium.
  • a directly heated oxide cathode is produced by using the base metal plate material of the present invention and coating an oxide layer conventionally used, e.g. by using a ternary carbonate mixture comprising BaCO 3 , SrCO 3 and CaCO 3 , there is no peeling of the oxide layer from the base and there can be obtained a quick operating type directly heated oxide cathode excellent in mechanical strength at high temperatures and specific electric resistance.
  • An alloy ingot containing 12% of rhenium, 4% of tungsten, 0.4% of zirconium and the remainder nickel was produced according to a standard powder metallurgy process, and a base metal plate of 30 ⁇ m in thickness was formed by cold rolling while the ingot was subjected to vacuum annealing repeatedly.
  • a ternary carbonate mixture of barium, strontium and calcium was coated on the base metal plate thus obtained and subjected to heat treatment at 1000° C. for 10 hours under vacuum to convert the carbonates into the oxides.
  • Adhesive strength of the oxide layer was examined under vacuum by scratching with a pin, and no peeling was produced. The sample was taken out into the air and after removing the oxide layer, interface layers were analyzed by X-ray diffraction. Only an interface layer due to zirconium was detected and no interface layer due to tungsten was detected.
  • a base metal plate of 30 ⁇ m thick made of an alloy containing 27.5% of tungsten, 0.4% of zirconium and the remainder nickel was used as a base metal and examined in the same manner as mentioned above.
  • the oxide layer was peeled off.
  • the sample mentioned above was taken out into the air and after removing the oxide layer, interface layers were analyzed by X-ray diffraction. An interface layer due to tungsten as well as an interface layer due to zirconium were detected.
  • Run No. 1 Ni 81.6, Re 16, W 2, Zr 0.4 (% by weight) Run No. 2 Ni 81.2, Re 12, W 6, Zr 0.8
  • peeling of the oxide layer and formation of interface layers were examined.
  • no peeling of the oxide layer was produced and only interface layers due to zirconium were detected.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid Thermionic Cathode (AREA)

Abstract

Base metal plate materials comprising nickel as a main component, rhenium and tungsten, and if desired, a small amount of at least one reducing agent can be used for producing quick operating type directly heated oxide cathodes showing no peeling of the oxide layer from the base metal and having excellent mechanical strength at high temperatures and specific electric resistance.

Description

This invention relates to a base metal plate material for a directly heated oxide cathode.
A prior art and the invention and the advantages of the latter will be described in detail with reference to the attached drawing which shows a sectional view of the principal part of an example of directly heated oxide cathodes.
As a cathode for a television picture tube, there has been mainly used an indirectly heated cathode wherein a time required for the appearance of an image from the beginning of receiving a television signal is shortened by always allowing flow of a preheating electric current through a heater even during a non-operation period and by raising a heater current value to a rating value at the time of receiving the television signal. But recently, from the viewpoint of saving energy, a quick operating type cathode which requires no preheating but a short time from the beginning of a heater current flow to the appearance of the image has been required. In the indirectly heated cathode, it generally requires about 20 seconds from the beginning of a heater current flow to the appearance of the image in the case of no flow of a preheating current. On the other hand, in the directly heated cathode wherein a so-called oxide for electron emission is directly coated on a heating element, the time required for the appearance of the image from the beginning of a heating current flow can be shortened to 1 to 2 seconds if properly designed. Such a cathode is suitable for the quick operating type cathode.
In the drawing, numeral 1 denotes a base which is heated by the supply of an electric current, numeral 2 denotes terminals for supplying the electric current, and numeral 3 denotes a so-called oxide. In order to improve the quick operating property of the cathode, it is necessary to use as the base 1 a material having high specific electric resistance so as to consume much electric energy in a small part of the electric current path. In order to control the temperature of the base made of such a material as mentioned above within a temperature range suitable for an oxide cathode, the base should have a form which has a longer periphery with respect to the cross-sectional area surrounded by the periphery. Therefore, the base is preferably made, for example, of a thin strip of such a material as mentioned above having a thickness of 100 μm or less, more preferably 60 μm or less. Thus, the material for the base should have sufficient mechanical strength at high temperatures in order to maintain the form having such a cross-section as mentioned above within the cathode operating temperature range. Moreover, the base material should have, as one of its important properties, the property of being suitable for causing sufficient electrons for a long period of time to be emitted from one or more so-called oxides such as barium oxide or a mixture of barium oxide and other oxides of alkaline earth metals, e.g. Ca, Sr, etc. coated on the surface of the base.
As materials which almost meet such conditions, alloys containing nickel as a main component together with either one or both of tungsten and molybdenum which are excellent in heat resistance and trace amounts of one or more reducing agents have been used experimentally and experientially as a base metal for directly heated oxide cathodes (e.g. Japanese Patent Appln. Kokai (Laid-Open) Nos. 57771/77, 39054/78 and 39055/78). But when such alloys were used as the base, there arose many problems such as a large amount of a so-called interface layer due to tungsten or molybdenum being produced between the base and the oxide layer during the picture tube production process or the usage of the thus produced picture tube, and more often resulting in peeling of the oxide layer. On the other hand, the use of rhenium containing alloys as a base metal plate material is also disclosed in Symp. on Rhenium, May 3-4, 1960 Chicago III, Elsevier Publishing, pages 175-180; U.S. Pat. No. 2,858,207; and Advances in Electron Tube Techniques, pages 6-9, 1963. But these alloys are insufficient in performance such as to maintain an electron emissive ability of the oxide cathode.
It is an object of the present invention to provide base metal plate materials for directly heated oxide cathodes overcoming such defects as mentioned above. In order to attain such an object in the present invention, rhenium which does not form an interface layer by itself between the base and the oxide layer is added to a nickel-tungsten alloy for improving mechanical strength at high temperatures and specific electric resistance.
The present invention provides a base metal plate material for a directly heated oxide cathode which comprises nickel as a main component, rhenium and tungsten, and if desired, a small amount of at least one reducing agent.
In the present invention, the base metal plate is made of an alloy comprising nickel as a main component, rhenium and tungsten.
A preferable amount of rhenium in the alloy is in the range from 4 to 17% by weight. If the amount of rhenium is too low, mechanical strength at high temperatures and specific electric resistance of the base become insufficient, while if the amount of rhenium is too much, rhenium is to be precipitated in the course of repeating temperature rise and cooling.
A preferable amount of tungsten in the alloy is in the range from 1 to 6% by weight. The presence of tungsten in such a range as mentioned above does not cause formation of an interface layer due to tungsten and peeling of the oxide layer. Since tungsten functions in such a manner as to maintain an electron emissive ability of the oxide cathode after the exhaustion of the reducing agent if contained or from the beginning if the reducing agent is not contained, the presence of tungsten produces very desirable results. If the amount of tungsten is too low, the effect of tungsten as mentioned above is insufficient, while if the amount of tungsten is too much, an interface layer due to tungsten is to be formed.
More preferable amounts of rhenium and tungsten seem to be dependent on mutual effects of these components. For example, when the tungsten content is 6% by weight, a more preferable range of rhenium is from 4 to 14% by weight, and when the tungsten content is 1% by weight, a more preferable range of rhenium is from 9 to 17% by weight. Therefore, the amount of rhenium in the range from 9 to 14% by weight is more preferable irrespective of the tungsten content in the range of 1-6% by weight. More in detail, when the proportion of tungsten changes from 1 to 6% by weight, a lower limit of the more preferable range of rhenium changes from 9 to 4% by weight linearly, whereas an upper limit of the more preferable range of rhenium changes from 17 to 14% by weight linearly.
The amount of nickel in the alloy is the rest of the total of rhenium and tungsten.
The base metal alloy may further contain at least one reducing agent such as zirconium, magnesium, silicon, aluminum and the like. In the case of zirconium, it is preferable to use zirconium in an amount of 5-6% by weight or less based on the weight of the alloy. If the amount is too much, a eutectic having a lower melting point will be produced to lower mechanical strength at high temperatures. In the case of magnesium, silicon and aluminum, an impurity amount of one or more these reducing agents, corresponding to an amount contained in a conventional base metal for an oxide cathode as an impurity, can usually be used together with or without zirconium.
When a directly heated oxide cathode is produced by using the base metal plate material of the present invention and coating an oxide layer conventionally used, e.g. by using a ternary carbonate mixture comprising BaCO3, SrCO3 and CaCO3, there is no peeling of the oxide layer from the base and there can be obtained a quick operating type directly heated oxide cathode excellent in mechanical strength at high temperatures and specific electric resistance.
The present invention will be explained in detail by way of the following Examples, in which all percents are by weight unless otherwise specified.
EXAMPLE 1
An alloy ingot containing 12% of rhenium, 4% of tungsten, 0.4% of zirconium and the remainder nickel was produced according to a standard powder metallurgy process, and a base metal plate of 30 μm in thickness was formed by cold rolling while the ingot was subjected to vacuum annealing repeatedly. A ternary carbonate mixture of barium, strontium and calcium was coated on the base metal plate thus obtained and subjected to heat treatment at 1000° C. for 10 hours under vacuum to convert the carbonates into the oxides. Adhesive strength of the oxide layer was examined under vacuum by scratching with a pin, and no peeling was produced. The sample was taken out into the air and after removing the oxide layer, interface layers were analyzed by X-ray diffraction. Only an interface layer due to zirconium was detected and no interface layer due to tungsten was detected.
For comparison, a base metal plate of 30 μm thick made of an alloy containing 27.5% of tungsten, 0.4% of zirconium and the remainder nickel was used as a base metal and examined in the same manner as mentioned above. The oxide layer was peeled off. The sample mentioned above was taken out into the air and after removing the oxide layer, interface layers were analyzed by X-ray diffraction. An interface layer due to tungsten as well as an interface layer due to zirconium were detected.
EXAMPLE 2
In the same manner as described in Example 1, the following alloy ingots were used for producing base metal plate.
Run No. 1 Ni 81.6, Re 16, W 2, Zr 0.4 (% by weight) Run No. 2 Ni 81.2, Re 12, W 6, Zr 0.8 In the same manner as described in Example 1, peeling of the oxide layer and formation of interface layers were examined. In individual Run Nos. 1 and 2, no peeling of the oxide layer was produced and only interface layers due to zirconium were detected.

Claims (7)

What is claimed is:
1. A base metal plate material for a directly heated oxide cathode which comprises an alloy containing rhenium in the range from 4 to 17% by weight, tungsten in the range from 1 to 6% by weight and the remainder being nickel.
2. A base metal plate material according to claim 1, wherein the amount of rhenium is in the range from 9 to 14% by weight, the amount of tungsten is in the range from 1 to 6% by weight, and the remainder is nickel.
3. A base metal plate material according to claim 1, wherein said base metal plate material has a thickness of 100 μm or less.
4. A base metal plate material according to claim 1 wherein said alloy further contains up to 6% by weight of at least one reducing agent selected from a group consisting of zirconium, magnesium, silicon and aluminum.
5. A base metal plate material according to claim 4, wherein the reducing agent is 6% by weight or less of zirconium.
6. A base metal plate material according to claim 4, wherein said at least one reducing agent is an impurity amount of magnesium, silicon and/or aluminum.
7. A base metal plate material according to claim 5, wherein zirconium is used in an amount of 0.4 to 0.8% by weight.
US05/961,272 1977-11-18 1978-11-16 Nickel alloy base metal plate for directly heated oxide cathodes Expired - Lifetime US4208208A (en)

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JP13790877A JPS5471550A (en) 1977-11-18 1977-11-18 Base metal material for direct heating oxide cathode
JP52-137908 1977-11-18

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NL (1) NL7811339A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4291252A (en) * 1978-11-29 1981-09-22 Hitachi, Ltd. Electron tube cathode
US4294606A (en) * 1977-04-15 1981-10-13 Ciba-Geigy Corporation Novel N-phenyl-substituted N-heterocyclic compounds, their preparation and use in agents for regulating plant growth
US4349766A (en) * 1979-04-28 1982-09-14 Hitachi, Ltd. Directly heated cathode for electron tube
US4928034A (en) * 1986-06-06 1990-05-22 Kabushiki Kaisha Toshiba Impregnated cathode
US20110020169A1 (en) * 2008-04-30 2011-01-27 Sanyo Special Steel Co., Ltd. Sputtering Target Material for Producing Intermediate Layer Film of Perpendicular Magnetic Recording Medium and Thin Film Produced by Using the Same

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2720458A (en) * 1952-04-29 1955-10-11 Sylvania Electric Prod Nickel-tungsten-aluminum alloy for cathode structure
US2833647A (en) * 1957-03-07 1958-05-06 Superior Tube Co Tungsten-zirconium-nickel cathodes
US2858207A (en) * 1954-12-24 1958-10-28 Charles Bertolus Ets Thermionic cathode cores composed of nickel-rhenium alloy
US3674710A (en) * 1969-05-10 1972-07-04 Siemens Ag Raney mixed catalyst
US3745403A (en) * 1971-11-30 1973-07-10 Hitachi Ltd Direct heating cathode structure for electron tubes
US3902093A (en) * 1973-04-06 1975-08-26 Int Standard Electric Corp Cathode heater element with a dark heat radiating coating and method of producing such
US3922428A (en) * 1972-02-04 1975-11-25 Spectra Mat Inc Thermionic cathode comprising mixture of barium oxide, calcium oxide and samarium oxide
US4079164A (en) * 1975-11-07 1978-03-14 Hitachi, Ltd. Base metal plate for directly heated oxide cathode
US4081713A (en) * 1976-01-28 1978-03-28 Hitachi, Ltd. Directly heated oxide cathode

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2720458A (en) * 1952-04-29 1955-10-11 Sylvania Electric Prod Nickel-tungsten-aluminum alloy for cathode structure
US2858207A (en) * 1954-12-24 1958-10-28 Charles Bertolus Ets Thermionic cathode cores composed of nickel-rhenium alloy
US2833647A (en) * 1957-03-07 1958-05-06 Superior Tube Co Tungsten-zirconium-nickel cathodes
US3674710A (en) * 1969-05-10 1972-07-04 Siemens Ag Raney mixed catalyst
US3745403A (en) * 1971-11-30 1973-07-10 Hitachi Ltd Direct heating cathode structure for electron tubes
US3922428A (en) * 1972-02-04 1975-11-25 Spectra Mat Inc Thermionic cathode comprising mixture of barium oxide, calcium oxide and samarium oxide
US3902093A (en) * 1973-04-06 1975-08-26 Int Standard Electric Corp Cathode heater element with a dark heat radiating coating and method of producing such
US4079164A (en) * 1975-11-07 1978-03-14 Hitachi, Ltd. Base metal plate for directly heated oxide cathode
US4081713A (en) * 1976-01-28 1978-03-28 Hitachi, Ltd. Directly heated oxide cathode

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294606A (en) * 1977-04-15 1981-10-13 Ciba-Geigy Corporation Novel N-phenyl-substituted N-heterocyclic compounds, their preparation and use in agents for regulating plant growth
US4291252A (en) * 1978-11-29 1981-09-22 Hitachi, Ltd. Electron tube cathode
US4349766A (en) * 1979-04-28 1982-09-14 Hitachi, Ltd. Directly heated cathode for electron tube
US4928034A (en) * 1986-06-06 1990-05-22 Kabushiki Kaisha Toshiba Impregnated cathode
US20110020169A1 (en) * 2008-04-30 2011-01-27 Sanyo Special Steel Co., Ltd. Sputtering Target Material for Producing Intermediate Layer Film of Perpendicular Magnetic Recording Medium and Thin Film Produced by Using the Same
US9293166B2 (en) * 2008-04-30 2016-03-22 Sanyo Special Steel Co., Ltd. Sputtering target material for producing intermediate layer film of perpendicular magnetic recording medium and thin film produced by using the same

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GB2011702A (en) 1979-07-11
GB2011702B (en) 1982-09-08
JPS5471550A (en) 1979-06-08
DE2849606C3 (en) 1982-02-25
DE2849606B2 (en) 1981-07-02
FI783504A (en) 1979-05-19
NL7811339A (en) 1979-05-22
DE2849606A1 (en) 1980-05-23

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